Nu-caylamido fatty acid compounds



Feb. 8, 1955 u-r 2,701,809

N ACYLAMIDO FATTY ACID COMPOUNDS Filed Jan. 9, 1951 O/cic Acid and Acry/o N/fri/e (physical n /xfure) sf/rribq Concenfrafcd Sulfuric Acid Crude Reac fion M/lvlur poured or? f0 l ce fi/fcreo 9+l0-N-acry/am/nb Sfcar/c Acid INVENTOR. HER MA 1v P1. A u 7' CJa/WM ATTORNE Y United States Patent N ACYLAIVIIDD"FAT'EY *ACID COMPOUNDS Herman .Plaut, "Los ''Angeles, Calif.

Application Januaryr 9, .1951, Serial No. 205,119

'13 Claims. ,(Cl. 160-404) This .Iinventionrelates (to the preparation -.of. new and tuseful .polymerizable :N-acylamido .fatty acid compounds, .--and more-,particularlyto -such .compounds-.1n which the acyl groupiseitheracryl or methacryl. This invent on talso relates to.a=.-new and inexpensive-method for the preparation ofthese useful compounds. I

f It is .an object of this invention -to prepare compounds .that.areuseful in the preparation ofygreases-andsoaps.

It is another object of this invention to produce such compounds as. are susceptible tov polymerizat1on,. thereby to increase themolecular weight of the compounds so that higher melting points 'and altered solubihty are obtained. These properties are of particular usefulness 1n the preparation of greases, but are valued as well in the preparation of thickening agents and stabrhzers.

It'is1also.anobject of this:inventi'on'.-to prepare: N- acyIamidoifattyI acids chea-ply by. the: usevof inexpens ve ireagents andibylisimple procedures wh1ch .can:be.carr1ed toutmat or near roomztemperature andpressure, .thereby permitting the employment :.:of a simple and UZIJGXPBIISIVG equipment.

Theiobjectsfof the instant invention xarerrealizedcby. the

reaction ofzaniacrylo ormethacrylo: nitrile-witlr an :ethylenically I unsaturated 1: and sunconjugated fatty racld, tor a -secondary-tihydroxy fatty-tacid wvhereinathe secondary hyidroxyliradical rdoesanotireside oni. thezralpha' carbon: atom. The reaction is effected in the presence ofi -axconcentrated mineral sacid, this term cbei-ng .used 1 :herein n'n xthe :usual sense to mean such/acids as-sulfuric,. phosphorlc, boron trifluoride and similar acids. Isolation of the product is easily accomplished by drowning of the reaction mixture with water and filter-ing extracting, or otherwise separating the product.

It" has beendiscoveredin accordance with the-*mStant invention *that 'the reaction outl-ine'd above takes place readily when use-is made'offfatty aci'ds 'contammg -an ethylenic unsaturation or dou'ble bond,"either-at theend of the car-bon chain--i-'suoh as wi'thundecylenic aoid--or where the double"bond occursinithetmiddle portion of the chain-such as with oleicacid; but the reaction does not occur where "the unsaturation' is conjugated with the carbonyl group such-as :with acryllc acids, If a .hydroxy fatty .acidis used as the .starting mater1al, ..-the 'lhy'droxy ,group must .be located on .=a.;seco n;dary; carbon .atom,.since it hasbeenfoundthati the reactlon withgprl- .mary. alcohol istooislowito be-of,pract1cal value. The I hydroxyl group .can. not reside on the. alpha. carbon atom, since it .haslbeen found that .alpha-hy'droxyr'stearlc "acid and lactic acid are inoperative. However,'beta-hydroxy acids, such as: beta-hydroxy-caproic react. readily.

Where an ethylenically unsaturated fatty acid is used as a reactant, there 'are generally obta ined simultaneouslya mixture of two products. in .varylng proportions. When the unsaturation resides at .the-end of a;.ca'rbon chain, only'one product'has been Ifoundnamely, the secondary derivative. "Thus only IO N-methacryI-anndoundecylenic acid. In the case of the hydroxy fatty acids, the amino group enters the position previously occup1ed by the hydroxy group used in the starting material.

While mixtures of compounds are usually obtained when an ethylenically unsaturated fatty acid is used as a reactant, it has been found that such mixtures are not a disadvantage, but that they can be readily used together since the properties of the isomers are so similar. The isomers can be separated if desired by standard techniques such as chromatography.

. undecylenic acid is obtained from methacrylo-nitrile and The reaction desired. herein is not limited in .scope .by

.thelength of the fatty acidcarbon chain. "However, it .has -been. .found .that.'.fatty acids .containing between .11 131K122. carbon. atoms. react .to,.giveproducts whose proper- .tiesaretespecially desirable, and which-products are with- .in -.the .scope of the instant .invention.

[It has'been furtherfound that the react-ion is not limited '.t0 .the fatty acids alone,'but proceeds equally well with their derivatives. "The presence of impurities in the .starting materials,.such.as saturated fatty. acids, in no way detracts from .theelfectiveness of the instant invention.

simplifies gpurification. Following purlfication .of the grodugt, the polymer may readily be formed .therefrom' if esire The'manner ofaddition of the 'reagents'is not critical. -Any ":one :can be added to "-a' solution of the other two. 'Howeverfth'e addition of the-mineralacid to atsolutio'n .of the organic'reactants; is preferred.

The acrylamidoan'cl methacrylamido fatty :'acids and derivatives thereof; prepared herein can be polymerizedto molecules of higher'molecular-weightbythe use of 'high temperatures "or the ;use i of peroxide catalysts such :as "benzoyl peroxide. The products of 'such polymerization 'haveproper'ties useful in theproduction. of alkyd resins, greases, fstabillzers, and. similar compounds.

The following-examples are included herein inorder to facilitate a more I complete understanding of the instant invention. A number of variations in the'process are-in- "cluded"belovwin orderto illustratethe'scope of .the invention-"disclosed.

.Example .1.-A solution of 25 .ml. of concentrated sulfuric .acid was added ..slowly.with.-.stirring to 18.5 g. of undecylenic. acid. and S 5 -.4 a g. i of acrylov nit'rile .in. a .500 ml. 3-neckedzflask surroundedby anice bath. 'The-addition wasregulatedisoithatwthe .temperaturendfd not rise over 120 .C., i'Which :required approximately .one-half hour. The stirring-was continued for two'hoursdur-ing which time the temperature was allowed. to. reach 40 The reaction: mixture was i then poured I over 100 gmswof iceand the,product.extracted with 1'0O0'rrll.. ether. The ether was washed with .water, -.dried .over anhydrous sodium sulfate anditheyproduct obtained :by distillation of theet her. flheresidue was'recrystallized from benzone to give white needles of -10-N-acrylamido-undecanoic acld, M. P. 104105 C. Nitrogen analysis, calculated 5.48%, found 5.39%.

Example 2..A solution of 18.5 g. of undecyleniciacid andi617'g.'ofmethacrylo nitrile was added'slo-wly'with stirring to 30 ml. of boron trifiuoride'e'therate in ail500 ml. .3-necked flask surrounded by an ice bath. The addition was 'regulated *sotha-t thetemperature did no rise over ZQ" C.,which"required approximately one-half hour. The ,stirringwas continuedfor'two hours during which 'timefthe temperature -was allowedto reach35 C. "The freactionmixture was thenpoured over 100 gms. of ice. 'l000iml. ether was added. The ether waswashed with water, "dried rover anhydrous j'sodium sulfate, and "the product obtained by distillation of the ether. The residue was recrystallized from benzene to give white needles of 10-N-methacrylamido-undecanoic acid, M. P. 96 C. Nitrogen analysis: calculated 5.49%, found 5.41%.

Example 3.To a solution of 5.4 g. of acrylo nitrile m 25 ml. of sulfuric acid was added slowly with stirring 28 gms. of oleic acid. The solution was cooled in an ice bath so that the temperature did not rise above 20 C. After the oleic acid had all been added, the reaction mixture was stirred for an additional two hours. The temperature was not allowed to rise above 40 C. The reaction mixture was poured onto ice and the solid material washed well with water and the latter drained off. The product was melted, beaten with water, cooled, and the water drained off. The product, a mixture of 9-and 10-N- acrylamido-stearic acid, melts at 80-85 C. Nitrogen analysis: calculated 3.94%, found 4.01%.

Example 4.-A mixture of 31.6 g. of methyl 12-hydroxystearate and .4 g. of acrylo nitrile was added slowly with stirring to 25 cc. of concentrated sulfuric acid. The temperature was held below 25 C. by means of a water bath and allowed to rise to 50 C. after addition of the reactant. Stirring was maintained for two hours. The reaction mixture was poured onto ice and the product extracted with 500 ml. g. chloroform. The chloroform was washed with a dilute sodium bicarbonate solution and then with'water. It was then dried over anhydrous sodium sulfate and the chloroform removed by distillation under slightly reduced pressure. The residue, methyl 12-N- acrylamidostearate, was a soft wax melting at 50-55 C.

Example 5.A mixture of 26.1 g. of N-phenyl undecenoamide and 5.4 g. of acrylo nitrile was added slowly with stirring to 25 ml. of concentrated sulfuric acid maintained at 20 C. by an ice bath. After addition of the reactants, the reaction mixture was stirred for four hours holding the temperature below 30 C. The reaction mixture was poured onto ice and the solid material filtered off and washed with water. On recrystallizing from acetone, the N-acrylamid-o-N-phenyl undecanoamide melted at 148151 C. Nitrogen analysis: calculated, 8.48%, found 8.67%

Example 6.A solution of 25.5 g. of IO-N-acrylaminoundecanoic acid and 14 g. of thionyl chloride was allowed to stand for several hours with occasional shaking. 27 gms. of the reaction mixture was added to a solution of 9.3 g. of aniline in 100 ml. of anhydrous pyridine. The reaction mixture was allowed to stand for twenty-four hours and then poured into an ice water mixture. The solid precipitate was filtered off and crystallized from acetone. M. P. 149-151 C. A mixed melting point with the -N-acrylamido-N-phenylundecanoamide prepared in Example 5 gave no depression.

In addition to the compounds prepared in the above examples, the following compounds have been prepared by similar procedures:

Example Compound M. P.

10-N-acrylamidoundecanoamide 151-153 0. Methyl 10-N-acrylmidoundecanoate... 6365 0. Methyl 9 and lU-N-acrylarnldostearate.- 40 C. 12-N-acrylamidostearic acid 60 C. 10-N-methacrylamidoundccanoic acid- 95-96 C.

9 and 10-N-methacryloamidostearic acid 90-100 C.

Methgl10-N-methacrylamidoundeeanoic 65 0.

act

10-N-methacrylamidoundccanoamide- 132 0.

10-N-n1ethacryl0amido-N-phenylundec- 132C.

anoamide.

N-acrylarnido fish oil fatty acid, connoncrystalline taining fatty acids with and 22 oil-sludge. carbon atoms in the carbon chain.

N-methaerylamido fish oil fatty acids Do.

containing fatty acids with 20 and 22 carbon atoms in the carbon chain.

acyl group is a member selected from the group con- .0

sisting of: an acryl group and a methacryl group and the acid portion is a fatty acid substituent containing 11 to 18 (inclusive) carbon atoms, with the nltrogen atom residing on a secondary carbon atom separated by 7 to 10 (inclusive) carbon atoms from the carbonyl group; and wherein the carbonyl group is joined to a member selected from the group consisting of (1) a hydroxyl group, (2) an alkoxyl group, (3) an amino group.

6. The method of producing an N-acrylamidostearic acid compound which comprises reacting a hydroxystearic acid in which the hydroxyl group resides on a secondary carbon removed 7 to 10 (inclusive) carbon atoms from the carbonyl group with acrylo nitrile, in the presence of a strong mineral acid.

7. The method of producing an N-acyl amido acid compound which comprises reacting a fatty acid containing 11 to 18 carbon atoms and which forms carbonium ions in the presence of a strong mineral acid, with an acrylic nitrile of less than five carbons, in the presence of a strong mineral acid.

8. An acrylamido acid compound wherein the amino acid portion is a fatty acid substituent containing 11 to 18, inclusive, carbon atoms, with the nitrogen atom residing on a secondary carbon atom seperated by 7 to 10 (inclusive) carbon atoms from the carbonyl group; and wherein the carbonyl group is joined to a member selected from the group consisting of (1) a hydroxyl group, (2) an alkoxyl group, (3) an amino group.

9. An acrylamido acid compound of the formula:

wherein x may vary from 1 to 9, inclusive; y may vary from 7 to 15, inclusive; x+y may vary from 9 to 16, inclusive; and R is a member selected from the group consistmg of (1) a hydroxyl group, (2) an alkoxyl group, (3) an amino group.

10. An acrylamido acid compound wherein the acid portion is a fatty acid substituent containing 11 to 18, inclusive, carbon atoms, with the nitrogen atom residing on a secondary carbon atom separated by 7 to 10 (inclusive) carbon atoms from the carbonyl group; and whereln the carbonyl group is joined to a hydroxyl group.

11. An acrylamido acid compound of the formula:

H(CHr),(fH-(CH2),,|C|R

r O=C-CH=GH2 wherein x may vary from 1 to 9, inclusive; y may vary from 7 to 15, inclusive; x-i-y may vary from 9 to 16, inclusive; and R is a hydroxyl group.

12. 10-N-acrylamidoundecanoic acid. 13. An N-acylamido acid compound of the formula:

H(CH2)=-CH(CH2),JCi3-R EITT R O=C( J=CHg where x may vary from 1 to 9, inclusive, may vary from 7 to 15, lnclusive, x+y may vary from 9 to 16, inclusive; R is a member selected from the group consist ng of: a hydroxyl group, an alkoxyl group, an amino group, and R is a member selected from the group consisting of: hydrogen, a methyl group.

References Cited in the file of this patent UNITED STATES PATENTS 2,309,509 Howk et a1 Jan. 26, 1943 2,440,140 Bruson Apr. 20, 1948 2,573,673 Ritter Oct. 30, 1951 

13. AN N-ACYLAMIDO ACID COMPOUND OF THE FORMULA 